Polyelectrolytes as detergent builders

ABSTRACT

A non-polluting builder composition for cleansing purposes is described consisting of composite of a polyelectrolyte and the alkali metal salt of a weak acid. Such builder compositions can replace the phosphorous and nitrogen-containing builders previously used in cleansing and laundry detergents with regard to effectiveness in hard water at one-tenth and one-fifth the concentrations of such previously used builders. In hard water, such composite builders prevent the precipitation of insoluble calcium soaps which occurs in household and laundry detergent compositions utilizing either component alone as a builder. The previously noted stabilizing effects of the polyelectrolyte with regard to enzymes and bleaches is not decreased by the added components of these composite builders.

States Patent 1 Grifo I POLYELECTROLYTES AS DETERGENT BUILDERS [52] US.Cl 252/135, 252/89, 252/137, 252/DIG. 15, 252/99 [51] Int. Cl. Clld3/04, Cl 1d 11/00 [58] Field of Search 252/135, 137,89, DIG. 15

[56] References Cited UNITED STATES PATENTS 3,156,655 ll/1964 Bright252/DIG. 15 3,284,364 ll/1966 Siegele 252/89 X 3,308,067 3/1967 Diehl252/DIG. 15 3,535,258 10/1970 Sabatelli et a1. 252/105 3,623,991 ll/l971 Sabatelli et al, 252/99 X 3,700,599 10/1972 Mizuno et al 202/137X 451 Mar. 11, 1975 Primary Examiner-Mayer Weinblatt Attorney, Agent, orFirmWalter C. Kehm; Samson B. Leavitt; James N. Blauvelt [57] ABSTRACT Anon-polluting builder composition for cleansing purposes is describedconsisting of composite of a polyelectrolyte and the alkali metal saltof a weak acid. Such builder compositions can replace the phosphorousand nitrogen-containing builders previously used in cleansing andlaundry detergents with regard to effectiveness in hard water atone-tenth and one-fifth the concentrations of such previously usedbuilders. In hard water, such composite builders prevent theprecipitation of insoluble calcium soaps which occurs in household andlaundry detergent compositions utilizing either component alone as abuilder. The previously noted stabilizing effects of the polyelectrolytewith regard to enzymes and bleaches is not decreased by the addedcomponents of these composite builders.

2 Claims, N0 Drawings 1 POLYELECTROLYTES AS DETERGENT BUILDERS FIELD OFTHE INVENTION This invention relates to detergent compositions usefulfor household and laundry service and particularly relates to buildersfor such compositions that are devoid of pollutant or toxic potentials.The term builders refers to the class of compounds and compositionswhich improve detergency levels of synthetic detergents and soaps. Byutilizing builders, it is possible to prepare detergent compositionshaving superior detergency as measured by removal of dirt and superiorqualities with regard to the redeposition of the dirt that is loosenedduring the washing process. Additionally, by utilizing builders, it ispossible to reduce the final cost of the detergent compositions.

The exact mechanism by which builders achieve their function indetergent compositions is not well understood. Consequently, it is notpossible to predict classes of compounds or compositions which wouldtend to function as builders. Presently, two criteria are used forevaluating the effectiveness of builder compositions; detergency andanti-soild redeposition. Convenient objective means for measuring andevaluating these qualities will be describedbelow.

In the recent past, the most commonly used builder materials have beenthe water-soluble inorganic alakaline phosphates and polyphosphates. Atpresent, their usage is being interdicted. The phosphate ion is anutrient for algae which are a prime cause of eutrification of our lakesand waterways. The phosphate ion from laundry and household use ofdetergents appears to enhance the growth of algae and the suddenovergrowth of algae interferes with the ecological balance within thelakes and waterways into which such waste waters are discharged.

A recently commercialized builder material, nitrolotriacetic acid, hadbeen proposed as a replacement for phosphate builders such as thepolyphosphates. However, recent research has indicated the possibilityof birth defects in test animals after exposure to combinations ofnitrilotriacetic acid, which is a nitrogencontaining chelating agent,with certain toxic salts. It appears that this builder molecule in somemanner permits the transport of toxic cadmium and mercury through tissuemembranes. Consequently, this material is less than desirable forutilization in and around the normal household and for discharge intoour environmental waters.

It is consequently an object of this invention to furnish a builderwhich is at least as effective as phosphates for use in detergentcompositions.

It is a further object of this invention to provide a builder which isnon-toxic and contains neither nitrogen phosphorus as readily availablenutrient elements for the overgrowth of algae or other undesirableaquatic plants.

It is a further object of this invention to provide a builder which canbe utilized for the preparation of ecologically balanced detergentproducts.

The above objects are achieved by the utilization in cleansingcompositions, comprising detergents and builders, a builder that is acomposite of certain polyelcctrolytes and alkaline-reacting salts ofalkali metals with weak acids. The polyelectrolyte component of thecomposite builders of this invention are the copolymer of lower alkylvinyl ethers with maleic acid or its anhydride. Preferred is PVM/MA ofPolyvinyl methyl ether/Maleic Anhydride and its hydrolyzed product. Theanhydride copolymer has the configuration of:

OR "I where R is lower alkyl up to 6 carbon atoms. .r is greater than10, indicating polymers of molecule weight ranging from about 1,500 toin excess of 2,500,000. The anhydride copolymer is also useful in itshydrolyzed form and its salts. The hydrolyzed form, polyvinyl methylether/maleic acid has the following configuration:

l r1]. i. l

where R and x are as indicated above.

Viscosity measurements are commonly used as an in dication of theaverage molecular weight of the polymeric composition. The K value(Fikentscher) of any particular mixture of polymers is calculated fromviscosity data and is useful as an indication of the average molecularweight of such mixtures. Its determination is fully described in MODERNPLASTICS 23 No. 3, 157-161, 212, 214, 216, 218, (1945) and is defined as1,000 times k in the empirical relative viscosity equation:

wherein C is the concentration in grams per hundred cc. of polymersolution and 1 re] is the ratio of the viscosity of the solution to thatof pure solvent. The K values are reportedas 1,000 times the calculatedviscosity coefficient in order to avoid the use of decimals. Thepreferred interpolymers employed in the present invention have k valuesof from about 10 to about 200.

K values and specific viscosities (1 sp) are interconvertible and arerelated through relative viscosity (n0 rel). Thus, when viscositymeasurements are taken on solutions which have a concentration of 1.00gram of polymer per deciliter of solution at 25C (C l), therelationships are as follows:

(log e nrel)/C and intrinsic viscosity (the limit of inherent viscosityas C approaches 0 have the dimensions of dilution, i.e., the reciprocalof concentration. Intrinsic viscosity and Viscosity Average MolecularGantrez 17 sp.* Weight AN-l l9 O.l 0.5 250,000 AN-l39 1.0 1.4 500,000AN-l49 l.5 2.0 750,000 AN-l69 2.6 3.5 1,250,000 AN-l 79 3.6 4.52,250,000

as determined on a solution of 1.0 gm. of the copelymcr in l ml ofmethyl ethyl ketene at 25C.

The two essential ingredients for cleansing compositions comprise thedetergent compound itself and the builder. Among the detergentcompositions useful in conjunction with the builders of this inventionare any of the classes of detergents commonly used for laundry andhousehold cleansers. These fall into the general classes of nonionic,anionic, cationic, and amphoteric detergents. Detergents from naturaland synthetic sources falling within these classes are amply set forthin Detergents and Emulsifiers, J. W. McCutcheon, editor, published by J.W. McCutcheon, Inc., 236 Mount Kemble Ave., West Orange, NJ.

The nonionic detergents as the name implies, are those which do notionize in water solution. Among the nonionic synthetic detergentscommonly used are those formed by the condensation reaction of ethyleneoxide units with hydrophobic bases among which are ethylene oxidecondensates with alkyl phenols wherein the alkyl group on the phenolcontains from six to about 12 carbon atoms in either straight orbranched-chain configuration and the ethylene oxide is present inamounts equal to 10 or 12 units of ethylene oxide per mole of alkylphenol. Further nonionic detergents are the group of aliphatic alcoholscondensed with ethylene oxide, i.e., alcohols having eight to 18 carbonatoms condensed with 8 to 30 units of ethylene oxide among which may bementioned the condensate of 10 to 30 moles of ethylene oxide withcoconut alcohol fractions having 10 to 14 carbon atoms. Other nonionicsynthetic detergents include the condensation products of ethylene oxidewith propylene oxide and diamines or phosphates and the long-chaintertiary amines, oxides and tcrtiaryphosphines oxides. These areeschewed for the purposes of this invention for reasons of theirpollution proclivities.

The preferred nonionic detergents for the purposes of this invention arethe condensates of nonylphenol with ethylene oxide offered commerciallyunder the Igepal trademark by GAF Corporation, New York City.

Among the anionic detergent compounds useful in the compositions of thisinvention, there must be mentioned ordinary soap. This is the alkalimetal salts of long-chain fatty acids having at least 12 carbon atoms.Suitable soaps are the sodium, potassium and ammonium salts of fattyacids, derived from oils and fats from vegetable and animal sources.

Among the anionic synthetic detergent compounds are the water-solublesalts and particularly the alkali metal salts of organic sulfuricreaction products such as the sulfonates and sulfates of alkyl andalkaryl moieties containing from eight to about 22 carbon atoms in thealkyl portion of the radical. Commercially important are the linearalkyl sulfonate sodium salts such as sodium lauryl sulfonate and thesodium and potassium alkyl benzene sulfonates such as are described inU.S. Pat. Nos. 2,220,009 and 2,477,383.

While the builders of this invention may be utilized with the amphotericsynthetic detergents. it is preferred not to do so since they generallyfall within the broad class of amine derivatives and due to thechclating nature of most of such amphoteric compounds with heavy metals,it is preferred to avoid solubitized forms of such toxic materials inhousehold environments.

The cationic synthetic detergents are generally the quaternary ammoniumsalts. Here due to the particular nature of the quaternary ammoniumcompounds. i.e., their ready biodegradeability, an exception is madeconcerning the utilization of nitrogen-containing deterv gents forgeneral household purposes. These compounds are particularly useful dueto their cold water detergency characteristics. Particularly useful forcold water laundry detergents is Soromine CAZ (CAP Corporation) acationic complex polyalkyl amido imidezolinium sulfate. Usually thecationic detergents are unstable in the presence of alkaline pHsolutions but the cationic detergents are fully compatible with thepolyelectrolyte/alkaline salts composite builder of this invention. Theparticular composition composite builders of this invention possibly dueto the presence of the polyelectrolyte appear not to have this adverseeffect.

In general, the detergent and builder composite of the present inventionare utilized according to the following proportions:

composite builder parts by weight 5 to 70 surfactant parts by weight 5to The above tabulation is a representation of the proportions of theactive detergent to the composite builder in detergent cleansingcompositions according to this invention. Complete detergentcompositions, of course, contain many ancillary ingredients useful forother purposes but having little to do directly with the problem of soilremoval and the prevention of soil redeposition which combined indicatethe cleansing effectiveness of the cleansing compositions. Among aneil-,lary agents which may be included in complete detergent eleansing and/orlaundry compositions to adapt to certain specific applications, theremay be mentioned the optical brighteners, anti-corrosives, foamstabilizers, defoaming agents, soil-suspending agents, enzymes, bleachesand the like. The composite builder of this invention does not interferewith most of these ancillary materials.

The final detergent cleansers of this invention may be compounded asliquids or solids.

Additionally, there may be employed coloring materials, perfumes andcorrosion inhibitors. In general, the detergent cleansing concentratesin the proportions tabulated above, plus any ancillary agents are thendiluted with water to the extent ofSOO to 20,000 parts by weight ofwater. Water presents its own problems depending on the degree ofhardness and the presence of unwanted ions. Hardness is measured by theamount of calcium and magnesium ions. Such ions form insolublenon-detergent curds with long-chain fatty acids thereby preventing fullutilization of the detergent compounds. Other deleterious ions includeiron which inalkaline solution tends to deposit as iron hydroxide, whichupon drying and oxidizing leaves unsightly stains (rust spots) onlaundered materials.

For general commercial practical use, it is preferred that the ratio ofpolyelectrolytes to alkaline salts in the composite builder, accordingto this invention, should range from 1 to l00 to l to 2 parts by weight.When the builder is used in ecologically desirabledetergentcompositions, the ratio of the detergent compound in thecleanser to the builder should be in the range of 8 parts by weight ofthe detergent to one part by weight of the builder. To the other end ofthe range one part by tion is commercially marketed in various molecularweight ranges. The various grades of polyelectrolyte are soluble inwater and within the concentration and pH ranges set forth, themolecular weight has little or no effect upon the efficiacy of thebuilder compositions of-this invention. I

In order to exemplify the present invention and to comparativelydemonstrate the advantages thereof, a series of formulations wereprepared and standardized samples were washed in these formulations inorder to evaluate their detergency and antisoil redeposition properties.The procedure used to evaluate the detergency properties of the producttested was as follows:

The Terg-O-Tometer Detergency Test as described weight of the detergentto 100 parts by weight of the in Detergency Evaluation and Testing (J.C. Harris, composite builder of this invention. They may beforlnterscience Publishers, N.Y.) was utilized. Standard mulated assolid compositions in powder or shaped soiled cotton cloth was purchasedfrom Test Fabrics. form or In llquld COnCentrlC 0rm- Inc. and used as ameans of measuring detergency Table 1 below is a tabulation ofconcentration ranges pr p rties, of h preferred p ly r ly of this n n in, The formula used to calculate percent detergency is PVM/MA, thepreferred alkaline salts, and commercial given in Detergency Evaluationand Testing" (p. 105) detergent compounds to be formulated into acondenand is: sate so that as diluted, the concentrate is equivalent toindustrial household and laundry products used at 1.0 grams/liter: [(AE) B/(C B)] X 100 Detergency TABLE 1 Detergent Use Range Preferred 71 byWeight of Solution 7:

Poly (vinyl methyl ether/ maleic anhydride or Poly (vinyl methyl ether/maleic acid .001 5.0 .005 Alkali metal salts of weak acids NHL-CO" .00110.0 .050 Na sio, .00l 10.0 .005 Borax .00l l().() .005 Detergent .0055.0 .0100 Optional Additives (MC 0.0 L0 .0005 Optical Brightener 0.0 0.5.0003 Na -S() 0.0 10.0 .0292 Sodium bicarbonate 0.0 l0.0

lt should be noted that PVM/MA is the preferred polwhere yelectrolytebut that mixtures of the alkaline salts may also be used in combinationwith sodium carbonate for there is a synergism between thepolyelectrolyte and the sodium carbonate or silicate or borate asregards the measurement of detergency at the various degrees of waterhardness commonly encountered in the.

United States. In the Examples, Examples 1 and 7 show the detergency asa function of water hardness for soda ash and sodium silicatepolyelectrolyte (PVM/MA) and the synergism found in the salts with thispolyelectrolyte as measured in the Tcrg-OTometer Detergency Test as asdescribed in Detergency Evaluation and Testing" (J. C. Harris,lnterscience Publishers, N.Y.).

With the other commonly used polyelectrolytes, it has been found thatthe detergency effect with alkaline salts is merely additive. While suchother polyelectrolyte/alkaline salts composites are useful, they are notas commercially attractive or as competitively attractive or ascompetitively cleansing or ecologically desirable as the composites ofthis invention.

As noted. the preferred polyelectrolyte of this inven-,

A reflectance of soiled swatch after washing B reflectance of soiledswatch before washing C= reflectance of redeposition swatch beforewashing E net reduction in reflectance of redeposition swatch (beforewashing minus after washing) Whiteness is calculated according to aformula published in Measurements of the Appearance of Paint Finishes byR. S. Hunter (Official Digest, Vol. 35, No. 459, p. 250-365) where Ggreen filter reflectance B blue filter reflectance Standard soiledswatches together with unsoiled swatches were washed in theTerg-O-Tometer using a solution of the product in the designated waterhardness. After washing 20 minutes, the swatches were rinsed and irondried and then measured for reflectance using the Hunter D40reflectometer. The data was then subjected to the whiteness formula andthe detergency formula. The results are given in the tables with eachexample.

EXAMPLE 1 The detergency of the preferred components of the compositeaccording to this invention, i.e poly (vinyl EXAMPLE 3 This exampleillustrates a composition containing the anionic detergent dodecylbenzene sulfonate marketed water hardness. The results clearlyillustrate the deter- 5 by Arco Chemical Co. under the name Ultrawet60K.

Composition: Gantrez AN 119 .017r .0171

Na. CO;, .0571 .0571

Conditions Dist. Water Plus Composition (Without Surfactant) B. 25 ppmCuC1 .5 ppm FeCl 21.1 25.8 6.8 34.3

C. 100 ppm CaCl 5 ppm FeCl 7.4 7.9 13.5 25.0

D. 200 ppm CaCl- 5 ppm FeCL, 25.0 5.8 7.0 25.6

E. 300 ppm CaCI 5 ppm FeCl 35.0 4.7 16.2 34.2

F. 1000 ppm CaCl 5 ppm FeCL, -48.0 2l.7 -3.5 16.8

Composition Ultrawet 60K .03371 .03371 .03371 .03371 Gantrez AN] 19.0171 .0171 Na CO .0571 .0571

Conditions Dist. Water Plus 71 Dctergency With Ultrawet 60K A. 25 ppmCaCL 5 ppm FeCl B. 100 ppm CaCl:. 5 ppm FeCl; C. 300 ppm CiiCl-g. 5 ppmFeCL,

gency synergism resulting from the preferred builder composites of thisinvention.

EXAMPLE 2 This example illustrates the detergency improvement of acomplete detergent composition including a non- EXAMPLE 4 surfactantGAFAC RA600 (TM) marketed by SAP Corporation and which is a complexorganic phosphate ester based on linear alcohols.

Composition GAFAC RA600 .0271 .0271 .0271 .0271 Gantrez AN119 .0171.0171 Na CO .0571 .0571

Conditions Dist. Water Plus 71 Detergency with GAFAC A. 25 ppm CaCl- 5ppm FeCL, 32.7 31.6 37.4 37.2 B. 100 ppm CaCl- 5 ppm FeCl 28.1 25.1 42.339.8 C. 300 ppm CZlCl-g, 5 ppm FeCl;, 10.7 11.5 26.6 39.8

Composition 1gepa1 C0630 02% .02% .02% .02% Gantrez AN] 19 .0171 .0171Na CQ, .0571 .0571 Conditions Dist. Water Plus Detergency With IgepalC0630 A. 25 ppm CaCL. 5 ppm FeCL 24.7 40.2 19.2 53.6 B. 100 ppm CaCl 5ppm FeCl 28.3 4.8 21.1 51.1

EXAMPLE 5 ionic synthetic detergent lgepal C0630 (TM) mar- 55 keted byGAF Corporation and which is generically described as anonylphenol-ethylcne oxide condensation product according to US. Pat.Nos. 1,970,578 and This example illustrates the effectiveness of thebuilder composite of this invention with sodium oleatc or soap as theanionic detergent.

Conditions Dist. Water Plus Composition Na+ Oleate Gantrez ANl19 Na CO A25 ppm B. 100 ppm C. 300 ppm CaCl 5 ppm FeCl CaCl 5 ppm FeCL, CaC1 5 ppmFeCl EXAMPLE 8 I Use Detergency Builder Compounds Concentration/7r WaterHardness(ppm) Average Redeposition Sodium Tripolyphosphate (STPP) 0.2100 36.8 60.5 NTA 0.] 100 40.6 63.3 Sodium Carbonate 0.05 l00 33.5 60.2Sodium Sulfate 0.2 100 3!.5 04.3 Poly (vinyl methyl/maleic anhydride)(Gantrez AN-l49 pH 7.0) 0.02 100 33.5 67.l Poly (vinyl methyl/maleicanhydride) (Gantrez AN-l49 NaCO EXAMPLE 6 This example illustrates theeffectiveness of the builder composite of this invention with thecationic detergent Soromine CAZ-75(TM) marketed by GAF Corporation andwhich is a complex polyalkyl amido imidazolinium sulfate.

Wherever parts or percentages are mentioned, they are to be construed.as parts and percentages by weight. While the invention has beendemonstrated in the examples by certain specific formulations, suchexamples merely indicate exemplary modes and compositions but theinvention is not to be construed as limited to Composition SoromineCAZ'-75 0.026671 0.02667: 0.02667: v 0.026671 Oantrez ABl l9 .Ol7z .017:Nil co 05% 05% Conditions I Dist. Water Plus 7! Detergeney with SoromineCAZ'75 A. ppm CaCl- 5 ppm FeCL, 52.8 18.3 86.3 24.1

EXAMPLE 7 such as the sole preferred modes and compositions as Thisexample illustrates the effectiveness of the builder composite of thisinvention utilizing sodium meta silicates as the alkaline salt insteadof sodium carbonate. The detergency effect of the polyelectrolyte andthe Na SiO of the components ofthe builder com- 3 positc is synergistic.

all equivalents thereto are intended.

What is claimed is:

l. A process for producing an ecologically desirable detergentcomposition suitable for washing textiles,

Igepal C0630 Conditions Dist. Water Plus Detergency with SodiumMetasilicate 100 ppm CaCl 5 ppm FeCl 14.2

As can be seen from Example 1 and 7, the combination of the poly (vinylmethyl/maleie anhydride with sodium carbonate or sodium metasilicate ismore effective than either component alone. This performance is morenoticeable as the water hardness increases. Examples 2. 3. 4, 5 and 6,aside from their demonstration ofthe effectiveness and utility of thecomposite builder of this invention with nonionic. anionic and cationicdetergents. also demonstrate the synergistic performance of thepreferred polyelectrolyte of this invention with soda ash in totalformulation.

While the prime purpose of the builder composite of this invention is toprovide non-polluting builders for household. industrial and laundrypurposes, the novel builders may also serve not only to completelyreplace the phosphate and nitrogen-containing builders previously usedbut may also partially replace them during interim periods of productchange-over. Example 8 below is a comparison of detergency andredeposition data of the commonly used builders with the compositebuilder of this invention and its components:

comprising admixing, as essential ingredients, a detergent selected fromthe group consisting of nonionic, anionic, cationic and amphotericdetergents, together with a composite builder, as sole builder,consisting of a member selected from the group consisting of polyvinylmethyl ether/maleic anhydride, salts and hydrolysis products thereofhaving a K value of from 10 to about 200 and at least one alkali metalsalt selected from the group consisting of alkali metal carbonates,alkali metal silicates, and alkali metal borates wherein the ratio ofpolyvinyl methyl ether/maleic anhydride group member to alkali metalsalt group member is, in parts by weight, from 1:100 to l:2, the ratioof the detergent to the composite builder being, in parts by weight, 8:]to 1:100, whereby to produce an ecologically desirable detergentcomposition at least substantially devoid of non-polluting nitrogen andphosphorus.

2. A process according to claim 1 wherein said alkali metal salt issodium carbonate.

1. A process for producing an ecologically desirable detergentcomposition suitable for washing textiles, comprising admixing, asessential ingredients, a detergent selected from the group consisting ofnonionic, anionic, cationic and amphoteric detergents, together with acomposite builder, as sole builder, consisting of a member selected fromthe group consisting of polyvinyl methyl ether/maleic anhydride, saltsand hydrolysis products thereof having a K value of from 10 to about 200and at least one alkali metal salt selected from the group consisting ofalkali metal carbonates, alkali metal silicates, and alkali metalborates wherein the ratio of polyvinyl methyl ether/maleic anhydridegroup member to alkali metal salt group member is, in parts by weight,from 1:100 to 1:2, the ratio of the detergent to the composite builderbeing, in parts by weight, 8:1 to 1:100, whereby to produce anecologically desirable detergent composition at least substantiallydevoid of non-polluting nitrogen and phosphorus.
 1. A PROCESS FORPRODUCING AN ECOLOGICALLY DESIRABLE DETERGENT COMPOSITION SUITABLE FORWASHING TEXTILES, COMPRISING ADMIXING, AS ESSENTIAL INGREDIENTS, ADETERGENT SELECTED FROM THE GROUP CONSISTING OF NONIONIC, ANIONIC,CATIONIC AND AMPHOTERIC DETERGENTS, TOGETHER WITH A COMPOSITE BUILDER,AS SOLE BUILDER, CONSISTING OF A MEMBER SELECTED FROM THE GROUPCONSISTING OF POLYVINYL METHYL ETHER/MALEIC ANHYDRIDE, SALTS ANDHYDROLYSIS PRODUCTS THEREOF HAVING A K VALUE OF FROM 10 TO ABOUT 200 ANDAT LEAST ONE ALKALI METAL SALT SELECTED FROM THE GROUP CONSISTING OFALKALI METAL CARBONATES, ALKALI METAL SILICATES, AND ALKALI METALBORATES WHEREIN THE RATIO OF POLYVINYL METHYL ETHER/MALEIC ANHYDRIDEGROUP MEMBER TO ALKALI METAL SALT GROUP MEMBER IS, IN PARTS BY WEIGHT,FROM 1:100 TO 1:2, THE RATIO OF THE DETERGENT TO THE COMPOSITE BUILDERBEING, IN PARTS BY WEIGHT, 8:1 TO 1:100. WHEREBY TO PRODUCE ANECOLOGICALLY DESIRABLE DETERGENT COMPOSITION AT LEAST SUBSTANTIALLYDEVOID OF NON-POLLUTING NITROGEN AND PHOSPHORUS.